Indirect influence of eutrophication on air - water exchange fluxes, sinking fluxes, and occurrence of polycyclic aromatic hydrocarbons.

How eutrophication affects biogeochemical processes of hydrophobic organic contaminants (HOCs) in aquatic environments is a pending challenge. Although the direct influence of eutrophication on biogeochemical processes of HOCs in waters has been well addressed, the indirect influence of eutrophication on biogeochemical processes of HOCs remains largely unknown. Here we take the large shallow eutrophic Lake Taihu in China and polycyclic aromatic hydrocarbons (PAHs) as examples to provide novel knowledge on the indirect influence of eutrophication on air - water exchange fluxes, sinking fluxes, and occurrence of HOCs. The air - water exchange fluxes of individual PAHs varied dramatically at different sites in all studied seasons. The sinking flux of ΣPAH was 14 855.3 ± 1579.9, 3548.9 ± 650.6, and 5588.4 ± 530.7 ng m d in spring, summer, and winter. The corresponding concentration of ΣPAH in surface sediments was 713.1 ± 78.6, 339.7 ± 36.6, and 293.0 ± 35.2 ng g d.w. Our study for the first time suggested that recruitment of cyanobacteria from surface sediments to water column in spring reduced the concentrations of PAHs in surface sediments, but enhanced their concentrations in the bulk water column, and overwintering of cyanobacteria in winter enhanced the concentrations of PAHs in surface sediments. High pH induced indirectly by eutrophication decreased seasonal air - water exchange fluxes (enhanced net volatilization) of PAHs, reduced the aromaticity of surface sediments and the hydrophobicity of phytoplankton cell surface, and reduced the accumulation of PAHs in surface sediments and phytoplankton consequently. Sinking fluxes and daily loss of PAHs from the water column decreased with phytoplankton biomass because the fraction of organic matter sinking from the water column decreased with phytoplankton biomass. Our study provides novel complementary knowledge for the biological pump for HOCs, and has important implications for understanding the coupling between eutrophication and biogeochemical processes of HOCs in subtropical shallow eutrophic waters.